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TWI872145B - 形成包括氧化矽的結構之方法 - Google Patents

形成包括氧化矽的結構之方法 Download PDF

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TWI872145B
TWI872145B TW109138020A TW109138020A TWI872145B TW I872145 B TWI872145 B TW I872145B TW 109138020 A TW109138020 A TW 109138020A TW 109138020 A TW109138020 A TW 109138020A TW I872145 B TWI872145 B TW I872145B
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silane
bis
depositing
diethylamino
bemas
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TW202118891A (zh
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福田秀明
上田真也
木村和弘
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荷蘭商Ａｓｍ Ｉｐ私人控股有限公司
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Abstract

本揭示係用於沉積在基材表面上之方法。例示性方法包括使用循環沉積製程沉積氧化矽材料以及在沉積步驟及後沉積退火步驟之一或多者期間使材料回流。亦揭示包括材料層的結構。

Description

形成包括氧化矽的結構之方法
本揭露大致上係關於形成適於用在電子裝置之製造中的結構之方法。更具體地，本揭露之實例係關於包括氧化矽層的形成之方法。
在裝置（諸如半導體裝置）之製造期間，常係所欲的是在具有絕緣或介電材料之基材表面上填充特徵（例如，溝槽或間隙）。一些填充特徵的技術包括硼磷矽酸鹽玻璃(borophosphosilicate glass, BPSG)的沉積及回流。
自1970開始已報告在電子裝置的製造中使用BPSG。BPSG膜可使用若干化學氣相沉積(chemical vapor deposition, CVD)技術中之一者（諸如，大氣壓CVD (atmospheric-pressure CVD, APCVD)、減壓CVD (reduced-pressure CVD, RPCVD)、低壓CVD (low-pressure CVD, LPCVD)、電漿增強CVD(plasma-enhanced CVD, PECVD)、及類似者）。一旦經沉積，BPSG膜可例如在約700 °C至1000 °C的溫度下回流以例如填充間隙或溝槽。
雖然此類技術針對若干應用可運作良好，具體地，隨著欲填充之特徵的大小減小，使用傳統的BPSG CVD沉積技術填充特徵具有若干缺點。例如，CVD沉積BPSG展現相對不良的步階覆蓋，且因此可在所沉積的材料內形成孔洞。在使沉積材料回流之後，此類孔洞可餘留。此外，為了致力減少孔洞，使用相對高溫及長退火時間來回流BPSG材料。進一步地，CVD沉積BPSG之相對高的膜生長率使BPSG通常不適於填充nm級三維圖案的間隙。額外地，使用一些CVD沉積技術可導致底層受損及B與P從BPSG材料擴散至底層。
隨著裝置及特徵的大小持續減小，逐漸變得難以將習知的BPSG沉積及回流技術應用於製造製程。因此，所欲的是用於形成結構之改善方法，具體係針對在結構形成期間填充間隙之方法。
本節提出之任何討論（包括問題及解決方案之討論）僅為了提供本揭露背景之目的而包括在本揭露中，且不應視為承認討論之任何或全部內容在完成本發明時已知或以其他方式構成先前技術。
本揭露之各種實施例係關於形成適於用在裝置形成中的結構之方法。雖然在下文更詳細地討論本揭露之各種實施例應對先前方法及結構之缺點的方式，大致上，本揭露之例示性實施例提供用於填充基材表面上的特徵及/或用以形成包含矽及氧的層或膜（諸如，包含矽、氧、及硼、磷、及鍺之一或多者的膜）之改善方法。
根據本揭露之至少一實施例，一種用於在基材表面上之一或多個特徵內沉積材料之方法包括提供包含一或多個特徵之基材至反應室中；使用循環沉積製程沉積材料至一或多個特徵上，其中材料之化學式包含Si及O；及在沉積步驟及後沉積退火步驟之一或多者期間使材料回流。化學式進一步包含B、P、Ge、Na、C、Al、Mg、Ca、Sr、及/或Ba之一或多者。循環沉積製程可包括電漿增強循環沉積製程（諸如電漿增強原子層沉積(plasma-enhanced atomic layer deposition, PEALD)製程或混合式PEALD－電漿增強化學氣相沉積(PECVD)製程）。回流步驟期間之反應室內的溫度可小於700 °C或介於約400 °C與約700 °C之間（例如，介於約450 °C與約600 °C之間）。回流步驟可在包含惰性氣體之大氣（諸如，由惰性氣體組成或包含惰性氣體及另一氣體（諸如氧化劑（例如氧））之大氣）中執行。（例如，在包含氧化劑及/或惰性氣體之大氣中之）回流步驟期間，反應室內的壓力可係約0.1 Pa至約大氣壓。方法可包括在沉積材料之步驟之前之沉積氧化矽(SiOx )之層的步驟及/或在沉積材料之步驟之後之沉積氧化矽(SiOx )之層之步驟。額外或替代地，方法可包括在沉積材料之步驟之前之沉積氮化矽(Six Ny )之層的步驟及/或在沉積材料之步驟之後之沉積氮化矽(Six Ny )之層之步驟。
根據本揭露之至少一其他實施例，一種形成結構之方法包括提供基材至反應室中及使用循環沉積製程將材料沉積至基材上，其中材料之化學式包含B、Si、及O。方法可進一步包括退火步驟。退火步驟可在大氣中、在壓力下、及/或在如上文所述或本文於別處所述之溫度下執行。
根據本揭露之再進一步的例示性實施例，至少部分地根據本文所述之方法形成結構。
所屬技術領域中具有通常知識者將從已參照隨附圖式之某些實施例的下列詳細描述輕易明白這些及其他實施例；本發明並未受限於任何已揭示的（多個）特定實施例。
雖然在下文揭示某些實施例及實例，所屬技術領域中具有通常知識者將了解本發明延伸超出本發明及其明顯的修改與等同物之具體揭示的實施例及/或用途。因此，意欲使所揭示之本發明的範疇不應受下文所述之具體揭示實施例的限制。
本揭露大致上係關於沉積材料之方法、關於形成結構之方法、及關於使用上述方法形成之結構。舉實例而言，本文所述之方法可用以使用材料（諸如絕緣（例如介電質）材料）填充基材表面上之特徵（諸如間隙，例如溝槽或貫孔）。舉具體實例而言，材料的化學式可包括Si及O。如下文更詳細提出者，化學式可額外包括氮、硼、磷、鍺、鈉、碳、鋁、鎂、鈣、鍶、及/或鋇之一或多者（例如二或更多者、三或更多者、或類似者）。
在本揭露中，「氣體(gas)」可指在常溫及常壓下為氣體之材料、汽化固體、及/或汽化液體，並可取決於上下文由單一氣體或氣體混合物構成。有別於製程氣體的氣體（亦即，非通過氣體分配總成（諸如噴淋頭）、其他氣體分配裝置、或類似者引入的氣體）可用於例如密封反應空間，氣體包括密封氣體（諸如，稀有氣體）。在一些情況下（諸如在材料沉積之背景下），用語「前驅物(precursor)」可指參與生成另一化合物之化學反應的化合物，且具體係指構成膜基質或膜之主要架構的化合物，而用語「反應物(reactant)」可指在一些情況下有別於前驅物之化合物，其使前驅物活化、對前驅物進行改質、或催化前驅物之反應；當例如施加射頻(RF)功率時，反應物可提供元素（諸如，O、N、C）至膜基質，並成為膜基質之一部分。在一些情況下，用語前驅物(precursor)及反應物(reactant)可互換地使用。用語「惰性氣體(inert gas)」係指當施加RF功率時，在可察覺的程度上不參與化學反應的氣體及/或激發前驅物的氣體，但不像反應物，該惰性氣體無法在可察覺的程度上變為膜基質之一部分。
如本文所使用，用語「基材(substrate)」可指可用以形成或在其上可形成裝置、電路、或膜之任何（多個）下伏材料。基材可包括塊材（諸如矽（例如單晶矽））、其他IV族材料（諸如鍺）、或化合物半導體材料（諸如GaAs），並可包括上覆或下伏於塊材的一或多層。進一步地，基材可包括各種特徵（諸如間隙、凹部、貫孔、線、及類似者），上述特徵經形成在基材之層或塊材的至少一部分之內或之上。舉實例而言，一或多個特徵可具有約10 nm至約100 nm的寬度，約30 nm至約1000 nm的深度或高度，及/或約3至100或約3至約20的深寬比。
在一些實施例中，「膜(film)」係指在垂直於厚度方向的方向上延伸的層。在一些實施例中，「層(layer)」係指形成於表面上之具有某一厚度之結構或者膜或非膜結構之同義詞。膜或層可由具有某些特性之離散單一膜或層或者由多個膜或層構成，且相鄰膜或層之間的邊界可以明確或可以不明確，且可以基於或可以不基於物理、化學、及/或任何其他特性、形成製程或序列、及/或相鄰膜或層之功能或用途而建立。層或膜可係連續的或者不連續的。
如本文中所使用，用語「包含矽及氧的層(layer comprising silicon and oxygen)」或「氧化矽層(silicon oxide layer)」可指其化學式可表示為包括矽及氧的層。包含氧化矽的層可包括其他元素（諸如氮、硼、磷、鍺、鈉、碳、鋁、鎂、鈣、鍶、及/或鋇之一或多者）。
如本文中所使用，用語「結構(structure)」可指部分或完全製造的裝置結構。舉實例而言，結構可包括具有形成在其上之一或多個層及/或特徵的基材。
如本文中所使用，用語「循環沉積製程(cyclic deposition process)」可指氣相沉積製程，其中沉積循環（一般係複數個接續的沉積循環）係在製程室中實施。循環沉積製程可包括循環化學氣相沉積(CVD)及原子層沉積製程。循環沉積製程可包括一或多個循環，其（等）包括前驅物、反應物、及/或惰性氣體之電漿活化。
如本文中所使用，用語「原子層沉積(atomic layer deposition, ALD)」可指氣相沉積製程，其中沉積循環（一般係複數個接續的沉積循環）係在製程室中實施。一般而言，在各循環期間，前驅物係化學吸附至沉積表面（例如基材表面或先前沉積的下伏表面，諸如來自先前ALD循環的材料），形成不易與額外前驅物起反應的單層或次單層（亦即，自限制反應）。其後，可隨後將反應物（例如，另一前驅物或反應氣體）引入製程室中，以用於在沉積表面上將經化學吸附之前驅物轉化為所欲材料。一般而言，此反應物能夠進一步與前驅物起反應。進一步地，亦可在各循環期間利用沖洗步驟以從製程室移除任何過量前驅物及/或在轉化經化學吸附之前驅物之後從製程室移除任何過量反應物及/或反應副產物。進一步地，當使用（多個）前驅物組成物、反應性氣體、及沖洗（例如惰性載體）氣體的交替脈衝執行時，如本文中所使用之用語「原子層沉積(atomic layer deposition)」亦意指包括由相關用語指定的製程，諸如，化學氣相原子層沉積(chemical vapor atomic layer deposition)、原子層磊晶(atomic layer epitaxy, ALE)、分子束磊晶(molecular beam epitaxy, MBE)、氣體源MBE、或有機金屬MBE、及化學束磊晶。電漿增強ALD (PEALD)可指ALD製程，其中電漿係在ALD步驟之一或多者期間施加。
在本揭露中，變數之任兩個數字可構成變數之可工作範圍，且所指示之任何範圍可包括或排除端點。此外，所指示的變數之任何數值（不管該等數值是否以「約」來指示）可指精確值或近似值並包括等效值，且在一些實施例中可指平均值、中值、代表值、多數值等。進一步地，在本揭露中，於一些實施例中，用語「包括(including)」、「由……構成(constituted by)」、及「具有(having)」可獨立地指「一般或廣泛地包含(typically or broadly comprising)」、「包含(comprising)」、「基本上由……組成(consisting essentially of)」、或「由……組成(consisting of)」。在本揭露中，於一些實施例中，任何已定義之意義未必排除尋常及慣例意義。
在本揭露中，於一些實施例中，「連續地(continuously)」可指不中斷真空、在時間線上無中斷、無任何材料插入步驟、未改變處理條件、其後立即、作為下一步驟、或在兩結構間無有別於該兩結構之插入的離散物理或化學結構之一或多者。
現轉向圖式，圖1繪示結構100。結構100包括基材102及氧化矽（例如硼磷矽酸鹽玻璃）膜104。基材102包括特徵（例如溝槽或貫孔）106。如所繪示，氧化矽膜104包括孔洞108。當氧化矽膜以非保形方式（例如使用傳統CVD技術）沉積時，孔洞108可形成。高溫退火可用以移除孔洞108或減少孔洞108的大小。然而，此類高溫製程對許多應用而言可係非所欲的。結構100亦包括底層受損區域110。底層受損區域110可包括使基材或使另一層（例如先前所沉積之薄氧化矽或氮化矽層）受損。底層受損區域110可由可用以沉積氧化矽層之高功率電漿製程導致。
圖2繪示根據本揭露之例示性實施例之結構200。結構200包括基材202及氧化矽層204。結構200亦可包括（例如氧化物、氮化物、或氮氧化物，諸如氧化矽、氮化矽、或氮氧化矽）層206，其在氧化矽層204底下；及/或層208（例如氧化物、氮化物、或氮氧化物，諸如氧化矽、氮化矽、或氮氧化矽），其上覆於氧化矽層204。
基材202可相同或類似於基材102。氧化矽層204可根據本文所述之方法形成。如所繪示，氧化矽層204不包括縫或孔洞。並且，結構200包括下伏表面之相對少至無受損（例如，很少至無底層受損區域）。
除了矽及氧以外，氧化矽層204可包括氮、硼、磷、鍺、鈉、碳、鋁、鎂、鈣、鍶、及/或鋇之一或多者，且具體係B、P、及Ge之一或多者。舉實例而言，氧化矽層204可係或可包括硼磷矽酸鹽玻璃(BPSG)。
圖3繪示根據本揭露之例示性實施例之方法（例如，用於沉積材料之方法及/或形成結構之方法）。方法300包括下列步驟：提供基材（步驟302）、沉積材料（步驟304）、及使材料回流（步驟306）。
在步驟302期間，提供基材至反應器之反應室中。根據本揭露之實例，反應室可形成循環沉積反應器（諸如原子層沉積(ALD)反應器）的部分。適於與方法300併用之例示性單基材反應器包括經特定設計以執行ALD製程之反應器。例示性合適的批式ALD反應器可一次處理多個基材。方法300的各種步驟可在單一反應室內執行或者可在多個反應室（諸如具有叢集工具的反應室）內執行。可選地，包括反應室的反應器可具備加熱器，以藉由提高基材及/或反應物/前驅物之一或多者的溫度來活化反應。
在步驟302期間，可使基材達到所欲的溫度及/或可使反應室達到所欲的壓力（諸如合適於步驟304期間的溫度及/或壓力）。舉實例而言，反應室內之（例如，基材或基材支撐的）溫度可介於約室溫與約600 °C之間或約300 °C與約500 °C之間。反應室內的壓力可係約1 Torr至約30 Torr或約3 Torr至約7 Torr。
在步驟304期間，氧化矽層係沉積在基材上。用於在基材表面上沉積氧化矽層之例示性技術包括循環沉積製程（諸如ALD製程）。在一些實施例中，步驟304包括使用循環沉積製程（諸如循環CVD或ALD製程）在基材/特徵上沉積材料層。舉具體實例而言，材料層可使用PEALD沉積。
例示性循環或PEALD製程可包括下列子步驟：使基材暴露至矽前驅物、沖洗反應室、使基材暴露至反應物（例如電漿活化反應物）、沖洗反應室、及重複這些步驟，直到得到氧化矽層之初始所欲的厚度。反應室內及/或基座的溫度可相同或類似於步驟302期間的溫度。類似地，反應室內的壓力可如上文連同步驟302所述者。
使基材暴露至矽前驅物可包括提供矽前驅物至反應室，該矽前驅物係選自由下列之一或多者組成之群組：(二甲胺基)矽烷(dimethylamino)silane, DMAS)、雙(二甲胺基)矽烷(bis(dimethylamino)silane, BDMAS)、雙(二乙胺基)矽烷(bis(diethylamino)silane, BDEAS)、雙(乙甲胺基)矽烷(bis(ethylmethylamino)silane, BEMAS)、雙(三級丁胺基)矽烷(bis(tertbutylamino)silane, BTBAS)、三(二甲胺基)矽烷(tris(dimethylamino)silane, TDMAS)、四(二甲胺基)矽烷(tetrakis(dimethylamino)silane, TKDMAS)、四(乙氧基)矽烷(tetra(ethoxy)silane, TEOS)、三(三級丁氧基)矽醇(tris(tert-butoxy)silanol, TBOS)、三(三級戊氧基)矽醇(tris(tert-pentoxy)silanol, TPSOL)、及Si(CH3 )2 (OCH3 )2 、SiH(CH3 )3 、Si(CH3 )4 。矽前驅物從矽前驅物源至反應室的流量率可係約1E-5莫耳/秒至約5E-4莫耳/秒、約1E-4莫耳/秒至約2E-4莫耳/秒、或約1.0E-4莫耳/秒至約1.5E-4莫耳/秒。使基材暴露至矽前驅物之各子步驟的持續時間可係約0.05秒至約10秒、約0.1秒至約5秒、或約0.1秒至約1秒。
沖洗反應室的步驟可包括使惰性氣體流至反應室及/或在反應室內提供真空壓力。沖洗氣體至反應室的流量率可係約0.1 slm至約30 slm、約1 slm至約20 slm、或約5 slm至約10 slm。反應室內的壓力可相同或類似於上文連同步驟302所述之壓力。各沖洗子步驟的持續時間可係約0.1秒至約10秒、約0.2秒至約3秒、或約0.2秒至約1秒。
使基材暴露至反應物之子步驟可包括提供O2 、O3 、CO2 、及N2 O之一或多者至反應室。反應物從反應物源至反應室的流量率可係約1 slm至約20 slm、約1 slm至約10 slm、或約1 slm至約3 slm。使基材暴露至反應物之各子步驟的持續時間可係約0.05秒至約10秒、約0.1秒至約5秒、或約0.1秒至約1秒。根據本揭露之例示性態樣，藉由使反應物氣體（例如氧源氣體，諸如氧、或CO2 、N2 O、O3 ）暴露至例如射頻及/或微波電漿而形成活化（例如氧）物種。可使用直接電漿及/或遠端電漿以形成活化物種。在一些情況下，反應物可連續地流至反應室，且反應物可針對循環沉積製程週期性地活化。在這些情況下，針對各循環之用於電漿的導通時間可係約0.02秒至約10秒、約0.1秒至約5秒、或約0.1秒至約1秒。
重複步驟（步驟308）可重複若干次，直到得到所欲的膜厚度。進一步地，可在繼續進行至下一步驟之前重複各步驟、子步驟、或子步驟的子組合。
在循環CVD的情況下，反應物及前驅物可同時引入反應室中。反應物及/或反應副產物可如本文所述般進行沖洗。進一步地，可使用混合式CVD/PECVD-ALD/PEALD製程，其中反應物及前驅物可持續一段時間以氣相起反應，且其中發生一些ALD。
在步驟304期間，可提供額外的前驅物及/或反應物至反應室。例如，可在步驟304期間提供包含氮、硼、磷、鍺、鈉、碳、鋁、鎂、鈣、鍶、及/或鋇之一或多者的前驅物或反應物至反應室。這些額外的前驅物及/或反應物可與其他前驅物或反應物一起流至反應室或可分開地流至反應室。舉實例而言，硼前驅物可在步驟304期間流至反應室。硼前驅物可選自例如由三甲基硼酸鹽(trimethylborate, TMB)及三乙基硼酸鹽(triethylborate, TEB)組成之群組的一或多者。額外或替代地，可提供磷前驅物至反應室中。磷前驅物可選自例如由三甲基磷酸鹽(trimethylphosphate, TMPO)、三甲基亞磷酸鹽(trimethylphosphite, TMPI)、三乙基磷酸鹽(triethylphosphate, TEPO)、及三乙基亞磷酸鹽(triethylphosphite, TEPI)組成之群組的一或多者。額外或替代地，可提供鍺前驅物至反應室中。例示性鍺前驅物包括四(二甲胺基)鍺。可在步驟304期間提供上述之額外前驅物及反應物之任何組合至反應室。
根據本揭露之一些實例，可藉由控制例如Si源、B源、及P源之饋送次數的數目之比率來調諧硼、磷、鍺、及類似者之一或多者的濃度。例如，當Si及B及P之饋送次數的數目之比率為1:0:0時，所沉積的是純SiOx。所沉積的材料可在惰性大氣下以＞ 450 °C後退火，且因此，膜回流並達成間隙填充。由於B2 O3 －SiO2 系統的共熔點係438 °C，後退火（回流）溫度可係＞ 438 °C或＞ 450 °C。
一旦在步驟304期間沉積所欲的材料量，可使材料回流。雖然分開地繪示，步驟306可發生在步驟304期間。若步驟304及306至少部分地分開，步驟304及306可在相同反應室中或在不同反應室中執行。
根據本揭露之各種實施例，步驟306期間之反應室內的溫度係小於700 °C或介於約400 °C與約700 °C之間、小於600 °C或介於約400 °C與約600 °C之間、或介於約450 °C與約600 °C之間、或介於約400 °C與約650 °C之間。步驟306期間之反應室內的壓力可係約0.1 Pa及約大氣壓、約1E2 Pa至約1E5 Pa、或約1E3 Pa至約1E5 Pa。
在步驟306期間，反應室中的大氣可包括惰性氣體。在一些情況下，大氣亦可包括氧化劑（諸如氧）。在這些情況下，大氣可在惰性氣體中包括約0.1%至約100%、約1%至約100%的氧化劑。惰性氣體的流量率範圍可從約0.01 slm至約30 slm或約1 slm至約10 slm。步驟306期間之氧化劑的流量率範圍可從約0.01slm至約10slm、約0.01slm至約1slm。
雖然未分開地繪示，方法300可包括下列之一或多者：在沉積材料之步驟304之前的沉積氧化矽(SiOx )層之步驟、在沉積材料之步驟之後的沉積氧化矽(SiOx )層之步驟、在沉積材料之步驟304之前的沉積氮化矽(Six Ny )層之步驟、在沉積材料之步驟之後的沉積氮化矽(Six Ny )層之步驟、在沉積材料之步驟304之前的沉積氮氧化矽層之步驟、及/或在沉積材料之步驟304之後的沉積氮氧化矽層之步驟。氧化物、氮化物、及/或氮氧化物層可使用循環沉積製程（諸如ALD製程）沉積。進一步地，當在步驟304之後沉積一層時，此類層可在步驟306之前或之後沉積。
圖4繪示結構402、404，其等可分別在步驟304、306期間形成。結構402包括基材406，其可包括例如本文所述之任何基材材料。氧化矽層408係使用例如方法300之步驟304沉積至基材406上。在沉積材料之步驟304及使材料回流之步驟306（例如後沉積退火步驟）之一或多者期間，氧化矽層流動以形成經流動的氧化矽層410。可重複步驟304及306，以填充基材406內的特徵412及/或直到得到經沉積及流動的材料之所欲厚度。
圖5及圖6繪示經沉積至圖案化基材上之氧化矽（例如BPSG）膜之掃描穿透式電子顯微鏡影像。根據方法300沉積及回流氧化矽膜。如所示，經回流的材料不包括任何縫或孔洞。在所繪示之實例中，特徵的深寬比範圍係從約3至約4，且特徵開口係約15 nm。
本揭露之各種實例提供改善的方法及結構。改善的實例包括： Ÿ 由於相對低的回流溫度，例示性方法可用在生產線前端的半導體製程中。例示性方法可在圖案化基材上沉積高保形性氧化矽（例如BPSG）膜，使得可將減量的回流用於間隙填充；因此，可大大地減少後退火溫度及時間。 Ÿ 由於初始保形的沉積，可在高AR圖案上達成無孔洞間隙填充（例如，上覆於具有大於例如2、5、或介於約3與約50之間的深寬比之特徵）。 Ÿ 可顯著緩解或甚至排除導因於大氣中之化學不穩定的BPSG之BPSG間隙填充製程的腐蝕問題。 Ÿ 結構可包括氧化矽、氮化矽、及/或氮氧化矽層，該等層可使用保形循環製程沉積。因此，可減少BPSG的沉積。 Ÿ 可抑制可能在沉積步驟期間發生的底層受損。氧化矽、氮化矽、及/或氮氧化矽層之初始層可藉由例如PEALD以高保形性沉積在圖案上；此一層可抑制在BPSG材料之沉積期間可以其他方式發生的電漿受損。 Ÿ 可減少氧化矽層中的B（及/或其他元素）至底層的擴散。 Ÿ 可抑制圖案變形。由於BPSG的沉積可係最小而可降低BPSG膜的應力，且膜的大多數部分可由氧化矽、氮化矽、或類似者組成。亦可減少後退火溫度及時間，且因此抑制後退火期間的變形。 Ÿ 可執行PEALD及PECVD混合式製程，其可達成所欲的間隙填充性質、高運行率、及/或低化學品消耗量。例如，PEALD可僅用於間隙填充的一部分，且其他部分可係PECVD。
上文所述之本揭露之實例實施例並未限制本發明的範疇，因為這些實施例僅為本發明之實施例之實例。任何等效實施例係意欲屬於本發明之範疇內。實際上，除本文中所示及所述者以外，所屬技術領域中具有通常知識者可由本說明書明白本揭露之各種修改（諸如所述元件之替代可用組合）。此類修改及實施例亦意欲落在隨附之申請專利範圍的範疇內。
100:結構 102:基材 104:膜 106:特徵 108:孔洞 110:受損區域 200:結構 202:基材 204:氧化矽層 206:層 208:層 300:方法 302:步驟 304:步驟 306:步驟 308:步驟 402:結構 404:結構 406:基材 408:氧化矽層 410:氧化矽層 412:特徵
當結合下列說明圖式考慮時，可藉由參照實施方式及申請專利範圍而得到對本揭露之例示性實施例的更完整了解。 圖1繪示結構，其包括在經沉積於特徵內之材料內所形成的孔洞。 圖2繪示根據本揭露之至少一實施例之結構。 圖3繪示根據本揭露之至少一實施例之方法。 圖4繪示根據本揭露之至少一實施例之額外結構。 圖5及圖6繪示根據本揭露之至少一實施例形成之結構的掃描穿透式電子顯微鏡影像。 將理解，圖式中之元件係為了簡單及清楚起見而繪示且不一定按比例繪製。例如，圖式中的一些元件之尺寸可相對於其他元件誇大，以幫助提升對本揭露所繪示之實施例的瞭解。
300:方法
302:步驟
304:步驟
306:步驟
308:步驟

Claims (29)

  1. 一種用於在基材表面上之一或多個特徵內沉積材料之方法，該方法包含：提供包含該一或多個特徵之一基材至一反應室中；使用一循環沉積製程沉積一材料至該一或多個特徵上，其中該材料之一化學式包含矽及氧；及在該沉積步驟及一後沉積退火步驟之一或多者期間，在1Torr至約30Torr的壓力下，使該材料回流。
  2. 如請求項1所述之方法，其中該循環沉積製程包含一電漿增強循環沉積製程。
  3. 如請求項1所述之方法，其中該循環沉積製程包含一電漿增強原子層沉積(plasma-enhanced atomic layer deposition,PEALD)製程。
  4. 如請求項1所述之方法，其中該回流步驟期間之一溫度係小於700℃。
  5. 如請求項4所述之方法，其中該溫度係介於約450℃與約600℃之間。
  6. 如請求項1所述之方法，其中該等特徵之一深寬比係大於或等於2。
  7. 如請求項6所述之方法，其中該深寬比係介於約3與約50之間。
  8. 請求項1所述之方法，其中該回流步驟係在包含一惰性氣體之一大氣中執行。
  9. 如請求項8所述之方法，其中該回流步驟係在包含一惰性氣體及一氧化劑之一大氣中執行。
  10. 如請求項1所述之方法，其中該化學式進一步包含B、P、及Ge之一或多者。
  11. 如請求項10所述之方法，其中該材料包含硼磷矽酸鹽玻璃(borophosphosilicate glass,BPSG)。
  12. 如請求項1所述之方法，其進一步包含在該沉積該材料之步驟之前沉積氧化矽(SiOx)之一層之一步驟。
  13. 如請求項1所述之方法，其進一步包含在該沉積該材料之步驟之後沉積氧化矽(SiOx)之一層之一步驟。
  14. 如請求項1所述之方法，其進一步包含在該沉積該材料之步驟之前沉積氮化矽(SixNy)之一層之一步驟。
  15. 如請求項1所述之方法，其進一步包含在該沉積該材料之步驟之後沉積氮化矽(SixNy)之一層之一步驟。
  16. 如請求項1所述之方法，其中該沉積材料步驟包含一混合式PEALD一電漿增強化學氣相沉積(plasma enhanced chemical vapor deposition,PECVD)製程。
  17. 如請求項1所述之方法，其中在該沉積該材料之步驟期間，提供一矽前驅物至該反應室中。
  18. 如請求項17所述之方法，其中該矽前驅物係選自由下列組成之群組的一或多者：(二甲胺基)矽烷(dimethylamino)silane,DMAS)、雙(二甲胺基)矽烷(bis(dimethylamino)silane,BDMAS)、雙(二乙胺基)矽烷(bis(diethylamino)silane,BDEAS)、雙(乙甲胺基)矽烷(bis(ethylmethylamino)silane,BEMAS)、雙(三級丁胺基)矽烷(bis(tertbutylamino)silane,BTBAS)、三(二甲胺基)矽烷(tris(dimethylamino)silane,TDMAS)、四(二甲胺基)矽烷(tetrakis(dimethylamino)silane,TKDMAS)、四(乙氧基)矽烷(tetra(ethoxy)silane,TEOS)、三(三級丁氧基)矽醇(tris(tert-butoxy)silanol,TBOS)、三(三級戊氧基)矽醇(tris(tert-pentoxy)silanol,TPSOL)、及Si(CH3)2(OCH3)2、SiH(CH3)3、Si(CH3)4。
  19. 如請求項1所述之方法，其中在該沉積該材料之步驟期間，提供一硼前驅物至該反應室中。
  20. 如請求項19所述之方法，其中該硼前驅物係選自由三甲基硼酸鹽(trimethylborate,TMB)及三乙基硼酸鹽(triethylborate,TEB)組成之群組的一或多者。
  21. 如請求項1所述之方法，其中在該沉積該材料之步驟期間，提供一磷前驅物至該反應室中。
  22. 如請求項21所述之方法，其中該磷前驅物係選自由三甲基磷酸鹽(trimethylphosphate,TMPO)、三甲基亞磷酸鹽 (trimethylphosphite,TMPI)、三乙基磷酸鹽(triethylphosphate,TEPO)、及三乙基亞磷酸鹽(triethylphosphite,TEPI)組成之群組的一或多者。
  23. 如請求項1所述之方法，其中在該沉積該材料之步驟期間，提供一鍺前驅物至該反應室中。
  24. 如請求項23所述之方法，其中該鍺前驅物係選自由四(二甲胺基)鍺組成之群組。
  25. 如請求項1所述之方法，其中在該沉積該材料之步驟期間，提供一反應物。
  26. 如請求項25所述之方法，其中反應物活性物種係使用一遠端電漿及一直接電漿之一或多者由該反應物形成。
  27. 如請求項1所述之方法，其中該化學式進一步包含氮、硼、磷、鍺、鈉、碳、鋁、鎂、鈣、鍶、及/或鋇之一或多者。
  28. 一種形成一半導體結構之方法，該方法包含：提供一基材至一反應室中使用一循環沉積製程沉積一材料至該基材上，其中該材料之一化學式包含B、Si、及O；及在1Torr至約30Torr的壓力下回流該材料。
  29. 如請求項28所述之方法，其進一步包含在一小於700℃的溫度下退火該材料之一步驟。
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